Pyrazolecarboxamides, intermediates therefor and pest control agent comprising the same as active ingredients

ABSTRACT

The present invention provides novel compounds with fungicidal and bactericidal activity as well as insecticidal and miticidal activity, which are useful for controlling hazardous biological organisms and belong to pyrazolecarboxamides represented by the following formula (I):  
                 
 
wherein R 1  represents C 1 -C 5  alkyl; R 2  represents C 1 -C 5  alkyl, C 1 -C 5  haloalkyl, or the like; R 3  represents hydrogen or C 1 -C 3  alkyl; R 4  represents halogen, C 1 -C 5  alkyl or the like; n is an integer of 0 to 4; R 5  represents alkyl, haloalkyl, alkoxy, haloalkoxy or the like; n represents an integer of 1 to 5; and X represents hydrogen, C 1 -C 3  alkyl, C 1 -C 3  alkoxy, halogen, C 1 -C 3  haloalkoxy or nitro.

TECHNICAL FIELD

The present invention relates to novel pyrazolecarboxamides andintermediates therefor, and pest control agents comprising the same asan active ingredient. The novel pyrazolecarboxamides in accordance withthe present invention are useful as bactericides and fungicides,insecticides and miticides for agriculture, and horticulture andfloriculture.

BACKGROUND OF THE INVENTION

In the field of agriculture as well as horticulture and floriculture,various fungicides and bactericides, insecticides and miticides havebeen developed and used in a practical sense for the purpose ofcontrolling various hazardous insects and plant diseases. However, itcannot be said that agricultural chemicals for common use in the relatedart have been satisfactory in terms of, for example, effect, spectrumand residual effect or have satisfied the demand to reduce the numberand chemical dose to be applied.

Additionally, the emergence of hazardous insects and plant diseases withacquired resistance against agricultural chemicals for common use in therelated art is now problematic. For the cultivation of vegetables, fruittrees, flowers, teas, wheat, barley, oats, etc., rice plants and thelike, various hazardous insects with acquired resistance against diversetypes of insecticides of, for example, carbamate-series,pyrethroid-series, benzoyl urea-series, organic chloride-series, andorganic phosphorus-series and various pathological microorganisms andbacteria with acquired resistance against various types of fungicidesand bactericides of, for example, triazole-series, imidazole-series,pyrimidine-series, benzimidazole-series, dicarboximide-series, andphenylamide-series have emerged in various local regions. Therefore, ithas been very tough increasingly year by year to control these varioushazardous insects and pathological microorganisms and bacteria causingplant diseases, because of such emergence of these resistant hazardousinsects.

Thus, it has been consistently desired the development of a novelagricultural chemical of which a lower chemical dose can express asufficient effect on the control of various pathological microorganismsand bacteria and hazardous insects with acquired resistance againstinsecticides and fungicides and bactericides for agriculture andhorticulture and floriculture in the related art and which shows lessadverse effects on environment.

The present inventors found that N-benzylpyrazole-5-carboxamidederivatives had insecticidal and miticidal activity. Specifically, thepublication of JP-A-64-25763 discloses the following compound withinsecticidal and miticidal activity, and the like.

Additionally, the publication of JP-A-3-81266 discloses that thefollowing compound with phenoxy and the like have insecticidal andmiticidal activity.

However, Compound (III) with a structure similar to the compound of thepresent invention as disclosed in JP-A-64-25763 is so insufficient inview of the insecticidal and miticidal activity that the practicalapplicability of the compound is still low.

Meanwhile, a compound with both fungicidal and bactericidal activity andinsecticidal and miticidal activity is very useful for use inagriculture and horticulture and floriculture. Regarding fungicidal andbactericidal activity, it is known that only a compound with specificsubstituents among compounds described in JP-A-64-25763 has fungicidaland bactericidal activity (JP-A-3-206079).

An object of the present invention to provide a new substance with agreat effect on the control of various pathological microorganisms andbacteria and with usefulness in the control of insects and mites,particularly a highly safe substance with a great effect on the controlof various hazardous insects and pathological bacteria causing plantdiseases with acquired resistance against fungicides and bactericidesand insecticides in the related art, because such a lower chemical dosethereof can express these effects that problems of residual toxicity andenvironmental pollution can be reduced.

DISCLOSURE OF THE INVENTION

The inventors have investigated the problems described above.Consequently, the inventors have found that novel pyrazolecarboxamideswith a biphenyl backbone with substituents and with a specificcombination of substituents have fungicidal and bactericidal activityand insecticidal and miticidal activity meeting the features describedabove. Thus, the present invention has been achieved.

The present invention relates to a pyrazolecarboxamide represented bythe following formula (I):

-   -   wherein R¹ represents C₁-C₅ alkyl,    -   R² represents C₁-C₅ alkyl, C₁-C₅ haloalkyl, C₁-C₅ alkoxy or        C₁-C₅ haloalkoxy,    -   R³ represents hydrogen or C₁-C₃ alkyl,    -   R⁴ represents C₁-C₅ alkyl, C₁-C₅ haloalkyl, C₁-C₅ alkoxy, C₁-C₅        haloalkoxy or halogen,    -   m is an integer of 0 to 4;    -   R⁵ represents alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio,        haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl,        haloalkylsulfonyl, halogen, cyano, formyl, vinyl,        alkoxycarbonyl, baloalkoxycarbonyl, acetyl, hydroxycarbonyl,        alkylcarbamoyl or a group represented by    -   wherein R⁷ and R⁸ each represents hydrogen or C₁-C₅ alkyl,    -   n represents an integer of 1 to 5,    -   X represents hydrogen, C₁-C₃ alkyl, C₁-C₃ alkoxy, halogen, C₁-C₃        haloalkoxy or nitro, or    -   R² and X may be taken together to form        wherein R⁹ represents hydrogen or C₃-C₃ alkyl,    -   a pest control agents comprising the pyrazolecarboxamide as an        active ingredient,    -   a phenylbenzylamine as an intermediate for the        pyrazolecarboxamide, which is represented by the following        formula (II):    -   wherein R³, R⁴, m and n have the same meanings as defined in        formula (I); R represents haloalkyl or haloalkoxy, and    -   an acid addition salt thereof.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention is now described in detail below.

Pyrazolecarboxamides:

In the pyrazolecarboxamides represented by formula (I) in accordancewith the present invention, the substituent R¹ represents a linear orbranched C₁-C₅ alkyl such as methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-methylbutyl,3-methylbutyl, isopentyl, 2-ethylpropyl, neopentyl, 2,2-dimethylpropyl,or 2-methylisobutyl. Among these, methyl is preferable as thesubstituent R¹.

The substituent R² represents linear, branched or cyclic C₁-C₅ alkylsuch as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,isobutyl, tert-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, isopentyl,2-ethylpropyl, neopentyl, 2,2-dimethylpropyl, 2-methylisobutyl, orcyclopropyl; linear or branched C₁-C₅ haloalkyl such as fluoronethyl,chloromethyl, bromomethyl, difluoromethyl, difluoroethyl,trifluoromethyl, trichloromethyl, tribromomethyl, 2-fluoroethyl,2,2,2-trifluoroethyl, 1-(trifluoromethyl)ethyl,1,1,2,3,3,3-hexafluoropropyl, 2,2,3,3,3-pentafluoropropyl,2,2,3,3-tetratluoropropyl, 2,2,3,3,4,4,4-heptafluorobutyl, or2,2,3,3,4,4,5,5,5-nonafluoropentyl; linear or branched C₁-C₅ alkoxy suchas methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy,isobutoxy, tert-butoxy, n-pentoxy, 2-methylbutoxy, 3-methylbutoxy,isopentoxy, 2-ethylpropoxy, neopentoxy, 2,2-dimethylpropoxy, or2-methylisobutoxy; or linear or branched C₁-C₅ haloalkoxy such asdifluoromethoxy, trifluoromethoxy, fluoromethoxy, trichloromethoxy,tribromomethoxy, 2-fluoroethoxy, 2,2,2-trifluoroethoxy,2,2,2-trichloroethoxy, 1-(trifluoromethyl)ethoxy,1,1,2,3,3,3-hexafluoropropoxy, 2,2,3,3,3-pentafluoropropoxy, or2,2,3,3-tetrafluoropropoxy. Among these, linear C₁-C₃ alkyl ispreferable as the substituent R² Ethyl is particularly preferable.

The substituent R³ represents hydrogen; or linear or branched C₁-C₃alkyl such as methyl, ethyl, n-propyl, or isopropyl. Among these,hydrogen is preferable as the substituent R³.

The substituent R⁴ represents linear or branched C₁-C₅ alkyl such asmethyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl,tert-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, isopentyl,2-ethylpropyl, neopentyl, 2,2-dimethylpropyl, or 2-methylisobutyl;linear or branched C₁-C₅ haloalkyl such as fluoromethyl, chloromethyl,bromomethyl, difluoromethyl, difluoroethyl, trifluoromethyl,trichloromethyl, tribromomethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl,1-(trifluoromethyl)ethyl, 1,1,2,3,3,3-hexafluoropropyl,2,2,3,3,3-pentafluoropropyl, 2,2,3,3-tetrafluoropropyl,2,2,3,3,4,4,4-heptafluorobutyl, or 2,2,3,3,4,4,5,5,5-nonafluoropentyl;linear or branched C₁-C₅ alkoxy such as methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, sec-butoxy, isobutoxy, text-butoxy, n-pentoxy,2-methylbutoxy, 3-methylbutoxy, isopentoxy, 2-ethylpropoxy, neopentoxy,2,2-dimethylpropoxy, or 2-methylisobutoxy; linear or branched C₁-C₅haloalkoxy such as difluoromethoxy, trifluoromethoxy, fluoromethoxy,trichloromethoxy, tribromomethoxy, 2-fluoroethoxy,2,2,2-trifluoroethoxy, 2,2,2-trichloroethoxy, 1-(trifluoromethyl)ethoxy,1,1,2,3,3,3-hexafluoropropoxy, 2,2,3,3,3-pentafluoropropoxy, or2,2,3,3-tetrafluoropropoxy; or halogen such as fluorine, chlorine,bromine or iodine. Among these, halogen is preferable as the substituentR⁴.

The substituent R⁵ represents linear or branched alkyl such as methyl,ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, isobutyl,tert-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, isopentyl,2-ethylpropyl, neopentyl, 2,2-dimethylpropyl, 2-methylisobutyl, n-hexyl,n-heptyl or n-octyl; linear or branched haloalkyls such as fluoromethyl,chloromethyl, bromomethyl, difluoromethyl, difluoroethyl,trifluoromethyl, trichloromethyl, tribromomethyl, 2-fluoroethyl,2,2,2-trifluoroethyl, 1-(trifluoromethyl)ethyl,1,1,2,3,3,3-hexafluoropropyl, 2,2,3,3,3-pentafluoropropyl,2,2,3,3-tetrafluoropropyl, 2,2,3,3,4,4,4-heptafluoropropyl, or2,2,3,3,4,4,5,5,5-nonafluoropentyl; linear or branched alkoxys such asmethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy,tert-butoxy, n-pentoxy, 2-methylbutoxy, 3-methylbutoxy, isopentoxy,2-ethylpropoxy, neopentoxy, 2,2-dimethylpropoxy, 2-methylisobutoxy,n-hexyloxy, n-heptyloxy, or n-octyloxy; linear or branched haloalkoxysuch as difluoromethoxy, trifluoromethoxy, fluoromethoxy,trichloromethoxy, tribromoinethoxy, 2-fluoroethoxy,2,2,2-trifluoroethoxy, 2,2,2-trichloroethoxy, 1-(trifluoromethyl)ethoxy,1,1,2,3,3,3-hexafluoropropoxy, 2,2,3,3,3-pentafluoropropoxy,2,2,3,3-tetrafluoropropoxy, or 2,2,3,3,4,4,4-heptafluorobutoxy; linearor branched alkylthio such as methylthio, ethylthio, propylthio,isopropylthio, butylthio, sec-butylthio, isobutylthio, tert-butylthio,pentylthio, 2-methylbutylthio, 3-methylbutylthio, isopentylthio,2-ethylpropylthio, neopentylthio, 2,2-direthylpropylthio, or2-methylisobutylthio; haloalkylthio such as trifluoronethylthio,perfluoroethylthio, perfluoropropylthio, or 2,2,2-trifluoroethylthio;linear or branched alkylsulfinyl such as methylsulfinyl, ethylsulfinyl,propylsulfinyl, isopropylsulfinyl, butylsulfinyl, sec-butylsulfinyl,isobutylsulfinyl, tert-butylsulfinyl, pentylsulfinyl,2-methylbutylsulfinyl, 3-methylbutylsulfinyl, isopentylsulfinyl,2-ethylpropylsulfinyl, neopentylsulfinyl, 2,2-dimethylpropylsulfinyl or2-methylisobutylsulfinyl; haloalkylsulfinyl such astrifluoromethylsulfinyl or 2,2,2-trifluoroethylsulfinyl; linear orbranched alkylsulfonyl such as methylsulfonyl, ethylsulfonyl,propylsulfonyl, isopropylsulfonyl, butylsulfonyl, sec-butylsulfonyl,isobutylsulfonyl, text-butylsulfonyl, pentylsul fonyl,2-methylbutylsulfonyl, 3-methylbutylsulfonyl, isopentylsulfonyl,2-ethylpropylsulfonyl, neopentylsulfonyl, 2,2-dimethylpropylsulfonyl, or2-methylisobutylsulfonyl; haloalkylsulfonyl such as trifluorosulfonyl or2,2,2-trifluoroethylsulfonyl; halogen such as fluorine, chlorine,bromine or iodine; cyano; formyl; vinyl; linear or branchedalkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl,n-propoxycarbonyl, isopropoxycarbonyl or butoxycarbonyl;haloalkoxycarbonyl such as 2,2,2-trifluoromethoxycarbonyl or2,2,3,3,3-pentafluorpropoxycarbonyl; acetyl; hydroxycarbonyl;alkylcarbamoyl such as methylcarbamoyl, ethylcarbamoyl orpropylcarbamoyl; or a group represented by

Herein, the above R⁷ and R⁸ each represents hydrogen; or linear orbranched C₁-C₅ alkyl such as methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, isobutyl, or pentyl.

In the above R⁵, the alkyl and alkoxy have preferably C₁-C₈; thehaloalkyl, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl,haloalkylsulfinyl, alkylsulfonyl and haloalkylsulfonyl have preferablyC₁-C₅. The alkoxycarbonyl, haloalkoxycarbonyls, alkylcarbamoyls andgroup represented by

have preferably C₂-C₅, more preferably C₂-C₅.

Among these, the substituent R⁵ is preferably haloalkyl or haloalkoxy,more preferably C₁-C₅ haloalkyl or C₁-C₅ haloalkoxy, particularlypreferably trifluoromethoxy or difluoromethoxy. Additionally, thesubstituent is preferably positioned at the 4-position.

The substituent X represents hydrogen; linear or branched C₁-C₃ alkylsuch as methyl, ethyl, n-propyl, and isopropyl; linear or branched C₁-C₃alkoxy such as methoxy, ethoxy, n-propoxy, or isopropoxy; halogen suchas fluorine, chlorine, bromine, or iodine; C₁-C₃ haloalkoxy such asdifluoromethoxy, 2,2,2-trifluoroethoxy, or perfluoropropoxy; or nitro.Among these, the substituent X is preferably hydrogen.

Furthermore, R⁹ in the group

formed by R² and X together represents hydrogen; or C₁-C₃ alkyl such asmethyl, ethyl, n-propyl or isopropyl.

-   -   m is an integer of 0 to 4, preferably 0 to 2; and n is an        integer of 1 to 5, preferably 1 or 2.        Phenylbenzylamines:

Furthermore, the phenylbenzylamines represented by formula (II) and acidaddition salts thereof in accordance with the present invention arenovel intermediates for producing the pyrazolecarboxamides.

Herein, the substituents R³ and R⁴, m and n have the same meanings asdefined in formula (I).

The substituent R⁶ represents haloalkyl such as fluoromethyl,chloromethyl, bromomethyl, difluoromethyl, difluoroethyl,trifluoromethyl, trichloromethyl, tribromomethyl, 2-fluoroethyl,2,2,2-trifluoroethyl, 1-(trifluoromethyl)ethyl,1,1,2,3,3,3-hexafluoropropyl, 2,2,3,3,3-pentafluoropropyl,2,2,3,3-tetrafluoropropyl, 2,2,3,3,4,4,4-heptafluorobutyl, or2,2,3,3,4,9,5,5,5-nonafluoropentyl; or haloalkoxys such asdifluoromethoxy, trifluoromethoxy, fluoromethoxy, trichloromethoxy,tribromomethoxy, 2-fluoroethoxy, 2,2,2-trifluoroethoxy,2,2,2-trichloroethoxy, 1-(trifluoroimethyl)ethoxy,1,1,2,3,3,3-hexafluoropropoxy, 2,2,3,3,3-pentafluoropropxy,2,2,3,3-tetrafluoropropoxy, or 2,2,3,3,4,4,4-heptafluorobutoxy. Thehaloalkyl and haloalkoxy have preferably C₁-C₅.

The acid to be added to the phenylbenzylamines represented by formula(II) in accordance with the present invention includes carboxylic acidsuch as acetic acid, propionic acid, butyric acid, oxalic acid, adipicacid, dodecanedioic acid, lauric acid, stearic acid, trifluoroaceticacid, fumaric acid, maleic acid, benzoic acid, or phthalic acid;sulfonate such as methanesulfonic acid, 1,3-propanedisulfonic acid,p-toluenesulfonic acid, or dodecylbenzenesulfonic acid; and inorganicacid such as hydrochloric acid, sulfuric acid, nitric acid, or carbonicacid.

Production Process:

The compound represented by formula (I) in accordance with the presentinvention is a novel compound and can be produced, for example, by thefollowing reaction scheme.

(In the formula, R¹, R², R³, R⁴, R⁵, X, m and n have the same meaningsas described in formula (I).)

In other words, pyrazolecarboxylic acid chloride (IV) andphenylbenzylamine (V) are allowed to react in the presence or absence ofa base, preferably using a solvent at −10 to 50° C., preferably 0 to 25°C.

As the solvent, any solvent can be used, so long as it does not havedirect influence on the reaction. The solvent includes aromatichydrocarbons such as benzene, toluene and xylene; ketones such asacetone, methyl ethyl ketone, and methyl isobutyl ketone; halogenatedhydrocarbons such as chloroform and dichloromethane; water; esters suchas methyl acetate and ethyl acetate; and polar solvents such astetrahydrofuran, acetonitrile, dioxane, N,N-dimethylformamide,N-methylpyrrolidone, dimethyl sulfoxide, and pyridine.

The base includes alkali metal hydrides such as sodium hydride; alkalimetal hydroxides such as sodium hydroxide and potassium hydroxide;alkali metal carbonates such as sodium carbonate and potassiumcarbonate; inorganic salts; and amines such as pyridine andtriethylamine.

In order to isolate the objective compound of formula (I) after thereaction, the following procedures are carried out in case of using asolvent soluble in water: distilling off the solvent under reducedpressure, adding water to the resulting residue, extracting the residuein aromatic hydrocarbons insoluble in water such as benzene, toluene andxylene, halogenated hydrocarbons such as chloroform and dichloromethane,and esters such as ethyl acetate, rinsing the extract with a saturatedaqueous sodium chloride solution, drying the extract over desiccantssuch as anhydrous sodium sulfate or anhydrous magnesium sulfate and thendistilling off the solvents under reduced pressure. When a solventinsoluble in water is used, water is added to the reaction mixture,followed by separation; the resulting organic layer is rinsed with asaturated aqueous sodium chloride solution and dried over desiccantssuch as anhydrous sodium sulfate or magnesium sulfate, from which thesolvent is distilled off under reduced pressure. The residue recoveredafter distillation of the solvent is purified by recrystallization,suspending and rinsing, and column chromatography, so that the objectivecompound represented by formula (I) can be recovered.

The compound represented by formula (IV) as one raw material can besynthetically prepared, for example, by the method described inJP-A-64-25763.

The compound represented by formula (V) as one raw material can besynthetically prepared, for example, by the following method.(1) Reduction of Phenylbenzonitriles

(In the formula, R⁴, R⁵, in and n have the same meanings as described informula (I).)

Phenylbenzonitrile (VI) and hydrogen are allowed to react in thepresence of a metal catalyst and aqueous ammonia, preferably using anorganic solvent, at 0 to 100° C., preferably 25 to 50° C.

As the organic solvent, any organic solvent can be used, so long as itdoes not have directly influence on the reaction. The organic solventincludes alcohols such as methanol, ethanol and isopropanol; aromatichydrocarbons such as benzene, toluene and xylene; ketones such asacetone, methyl ethyl ketone, and methyl isobutyl ketone; halogenatedhydrocarbons such as chloroform and dichloromethane; water; esters suchas methyl acetate and ethyl acetate; or polar solvents such astetrahydrofuran, acetonitrile, dioxane, N,N-dimethylformamide,N-methylpyrrolidone, dimethyl sulfoxide, and pyridine.

The metal catalyst includes Raney-nickel, palladium carbon, and platinumoxide.

In order to isolate the objective compound of formula (Va) after thereaction, the metal catalyst is filtered off from the reaction mixture,and the solvent is distilled off from the resulting filtrate underreduced pressure. The resulting product may be sufficiently pure as itis, but the product can be purified by means of evaporation and columnchromatography, to recover a pure product.

Phenylbenzonitrile (VI) can be synthetically prepared by reaction of thecorresponding haloallene with phenylboronic acid in the presence of azero-valent palladium catalyst and a base according to known methods,for example, the method described in Synthetic Communications, Vol. 11,page 513 (1981).(2) Reduction of Oximes

Oxime (VII) and hydrogen are allowed to react in the presence of a metalcatalyst and aqueous ammonia, preferably using an organic solvent, at 0to 100° C., preferably 25 to 50° C.

As the organic solvent, any organic solvent can be used, so long as ithas not direct influence on the reaction. The organic solvent includesalcohols such as methanol, ethanol and isopropanol; aromatichydrocarbons such as benzene, toluene and xylene; ketones such asacetone, methyl ethyl ketone, and methyl isobutyl ketone; halogenatedhydrocarbons such as chloroform and dichlioromethane; water; esters suchas methyl acetate and ethyl acetate; and polar solvents such astetrahydrofuran, acetonitrile, dioxane, N,N-dimethylformamide,N-methylpyrrolidone, dimethyl sulfoxide, and pyridine.

The metal catalyst includes Raney-nickel, palladium carbon, and platinumoxide.

In order to isolate the objective compound of formula (Vb) after thereaction, the metal catalyst is filtered off from the reaction mixture,and the solvent is distilled off from the resulting filtrate underreduced pressure.

Oxime (VII) can be synthetically prepared by reaction of thecorresponding acetophenone with hydroxyamine in the presence ofpotassium carbonate according to known methods.

Phenylbenzylamine-acid addition salts (Vc) can be synthesized by thefollowing method.

Phenylbenzylamine (V) and acid (Y) are allowed to react, preferablyusing a solvent, at −5 to 50° C., preferably 0 to 25° C.

As the acid, organic acid and inorganic acid can be used. The organicacid includes carboxylic acids such as acetic acid, propionic acid,butyric acid, oxalic acid, adipic acid, dodecanedioic acid, lauric acid,stearic acid, trifluoroacetic acid, fumaric acid, maleic acid, benzoicacid, and phthalic acid; and sulfonates such as methanesulfonic acid,1,3-propanedisulfonic acid, p-toluenesulfonic acid, anddodecylbenzenesulfonic acid. The inorganic acid includes hydrochloricacid, sulfuric acid, nitric acid and carbonic acid.

As the solvent, any solvent can be used, so long as it does not havedirect influence on the reaction. The organic solvent includes aromatichydrocarbons such as benzene, toluene and xylene; ketones such asacetone, methyl ethyl ketone, and methyl isobutyl ketone; halogenatedhydrocarbons such as chloroform and dichloromethane; water; esters suchas methyl acetate and ethyl acetate; and polar solvents such astetrahydrofuran, acetonitrile, dioxane, N,N-dimethylformamide,N-methylpyrrolidone, dimethyl sulfoxide, and pyridine.

After the reaction, the solvent is distilled off under reduced pressure.The resulting crystals are filtered and recovered, to syntheticallyprepare inorganic acid salts of benzylamine and organic acid saltsthereof. The crystals are satisfactory as they are. For furtherpurification, however, the crystals are rinsed with the organic solventsdescribed above, to synthetically prepare benzylamine salts at highpurity.

Pest Control Agents:

The compound represented by formula (I) in accordance with the presentinvention has high fungicidal and bactericidal effects on pathologicalmicroorganisms and bacteria against plants such as Pyricularia oxyzae,pathological microorganisms and bacteria causing powdery mildew,pathological microorganisms and bacteria causing rust, and pathologicalmicroorganisms and bacteria causing downy mildew so that the compound isuseful as an active ingredient for fungicides and bactericides foragriculture and horticulture and floriculture. Since the compound of thepresent invention has high activity on the control of the eggs andlarvae of insects of the order Hemiptera including leafhoppers such asSogatella furcifera Horvath, Nilaparvata lugens (Stal), and Laodelphaxstratella (Fallen); Cicadomorpha-2 such as Bothrogonia ferruginea(Fabricius) and Cicadella viridis (Linnaeus); and Aphididae such asMyzus persicae; the order Lepidoptera including Spodoptera lituraFabricius, Chilo suppresalis, Cnaphalocrosis medinalis Guenee andPlutella xylostella (Linnaeus); the order Coleoptera includingCallosobruchus chinensis; the order Diptera including Musca domesticaLinnaeus, Aedes aegypti and Culex pipiens pallens; the order Orthoptera;and the order Acarina including Tetranychus urticae Koch, Tetranychuscinnabarinus (Boisduval) and Panonychus citri (Mcgregor), the compoundof the present invention is useful as an active ingredient forinsecticides and miticides for agriculture and horticulture andfloriculture. It is needless to say that the pathological microorganismsand bacteria against plants, insects, and mites as subjects to becontrolled with the compound of the present invention are not limited tothose described above.

When the compound represented by formula (I) in accordance with thepresent invention is used for fungicides and bactericides, insecticidesand/or miticides for agriculture and horticulture and floriculture, thecompound may satisfactorily be used singly. However, preferably, thecompound may be used in composition forms produced using agriculturalauxiliary agents for common use in the art, such as fungicides andbactericides, insecticides and/or miticide's for agriculture andhorticulture and floriculture. The forms are preferably, for example,emulsions, hydrates, powders, flowable agents, fine granules, granules,tablets, oils, sprays, and fumes. However, the forms are not limitedthereto. One or two or more forms of the compound may also be blended asactive ingredients.

The agricultural auxiliary agents for use in producing the fungicidesand bactericides, insecticides and/or miticides for agriculture andhorticulture and floriculture are used, for example, for the improvementof the effects of fungicides and bactericides, insecticides and/ormiticides for agriculture and horticulture and floriculture and for theimprovement of stability and dispersibility. For example, carriers(diluents), spreading agents, emulsifiers, wet spreading agents,dispersants and disintegrators can be used.

The liquid carriers include water, aromatic hydrocarbons such as tolueneand xylene, alcohols such as methanol, butanol, and glycol, ketones suchas acetone, amides such as dimethylformamide, sulfoxides such asdimethyl sulfoxide, methylnaphthalene, cyclohexane, animal and vegetableoils, and fatty acid. Additionally, the solid carriers include clay,kaolin, talc, diatomaceous earth, silica, calcium carbonate,montmollionite, bentonite, feldspar, quartz, alumina, sawdust,nitrocellulose, starch and gum arabic.

As the emulsifiers and the dispersants, general surfactants can be usedand include anionic surfactants, cationic surfactants, nonionicsurfactants and ampholytic surfactants, such as higher alcohol sodiumsulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenylether, and lauryl betaine. Additionally, the following agents can alsobe used: spreading agents such as polyoxyethylene nonyl phenyl ether andpolyoxyethylene lauryl phenyl ether; wet spreading agents such asdialkylsulfosuccinate; attaching agents such as carboxymethyl celluloseand polyvinyl alcohol; and disintegrators such as sodium ligninsulfonate and sodium lauryl sulfate.

The content of the active ingredient in the fungicides and bactericides,insecticides and/or miticides for agriculture and horticulture andfloriculture in accordance with the present invention is selected withina range of 0.1 to 99.5% and is appropriately determined on the basis ofvarious conditions for preparations and application methods. Preferably,for example, powders are produced so as to contain the active ingredientat about 00.5 to 20% by weight, preferably about 10% by weight; hydratesare produced so as to contain the active ingredient at about 1 to 90% byweight, preferably 10 to 80% by weight; emulsions are produced so as tocontain the active ingredient at about 1 to 90% by weight, preferablyabout 10 to 40% by weight.

In the case of the emulsions, for example, solvents, surfactants and thelike are mixed with the compound as the active ingredient to prepare astock emulsion. The stock emulsion is diluted with water to a givenconcentration when used, and is applied. The resulting solution can beapplied. In the case of the hydrates, the compound as the activeingredient, a solid carrier, a surfactant and the like are mixedtogether to prepare a stock solution. The stock solution is diluted withwater when used, and is applied. In the case of the powders, thecompound as the active ingredient, a solid carrier and the like aremixed together. The resulting mixture can be used as it is. In the caseof the granules, the compound as the active ingredient, a solid carrier,a surfactant and the like are mixed together and granulated, to preparegranules, which can be used as it is. It is needless to say that themethods for preparing the preparations are not limited to thosedescribed above. One skilled in the art can select an appropriatemethod, depending on the type of the active ingredient, the purpose ofapplication and the like.

In addition to the compound as the active ingredient, the fungicides andbactericides, the insecticides and/or miticides for agriculture andhorticulture and floriculture in accordance with the present inventionmay contain any appropriate active ingredients such as other fungicidesand bactericides, insecticides, miticides, herbicides, insect growthcontrolling agents, fertilizers, and soil modifiers. The method forapplying the fungicides and bactericides, insecticides and/or miticidesfor agriculture and horticulture and floriculture in accordance with thepresent invention is not particularly limited, and spraying on stem andleaf, application on water surface, soil treatment, and seed treatmentcan be carried out. In the case of spraying on stem and leaf, forexample, a solution within a concentration range of 5 to 1,000 ppm,preferably 10 to 500 ppm can be used at a volume of about 100 to 200liters per 10 Ares. For application on water surface, generally,granules at 5-15% content of the active ingredient are applied at aratio of 1 to 10 kg per 10 ares. In the case of soil treatment, asolution within a concentration range of 5 to 1,000 ppm is applied at aratio of about 1 to 10 liters per ², In the case of seed treatment, asolution within a concentration range of 10 to 1,000 ppm is applied at aratio of about 10 to 100 ml per kg of seeds.

The present invention is now described in the following examples in moredetail. However, the scope of the present invention is not limited tothe following examples.

EXAMPLES

The present invention is now described below in detail in the followingexamples, Formulation Examples and test examples. However, the presentinvention is not limited to the examples, unless the examples aredeparted from the scope of the present invention.

Example 1

N-[4-(4-Difluoromethoxyphenyl)benzyl]-1-methyl-3-ethylpyrazole-5-carboxamide:

A mixture of 4-(4-difluoromethoxyphenyl)benzylamine (13.8 g),triethylamine (10 ml) and dichloromethane (100 ml) was cooled to 0° C.to 4° C., followed by addition of a solution (20 ml) of1-methyl-3-ethylpyrazole-5-carboxylic acid chloride (12.4 g) indichloromethane, for agitation for 30 minutes. The reaction mixture waspoured into water (200 ml), for extraction in dichloromethane. Theorganic layer was rinsed with a saturated aqueous sodium chloridesolution and dried over anhydrous sodium sulfate. The solvent wasdistilled off under reduced pressure. The resulting residue was purifiedby silica gel chromatography, to obtain 17.0 g of Compound No. 30described in Table-1. The melting point was 107 to 108° C.

Example 2

According to the method in Example 1, the compounds described in Table-1were prepared synthetically. TABLE 1

Compound No. R¹ R² X R³

m.p.(° C.) or nD/(° C.) 1 CH₃ CH₃ CH₃ H

162-163 2 CH₃ CH₃ C₂H₅O H

1.5464/23.0 3 CH₃ CH₃ H H

128-130 4 CH₃ CH₃ H H

98-99 5 CH₃ CH₃ H H

134-135 6 CH₃ CH₃ H H

127-128 7 CH₃ CH₃ H H

122-124 8 CH₃ C₂H₅ H H

116-118 9 CH₃ C₂H₅ H H

119-121 10 CH₃ C₂H₅ H H

106-107 11 CH₃ C₂H₅ H H

104-108 12 CH₃ C₂H₅ H H

105-107 13 CH₃ C₂H₅ H H

110-111 14 CH₃ C₂H₅ H H

90-91 15 CH₃ C₂H₅ H H

95-97 16 CH₃ C₂H₅ H H

1.5671/23.0 17 CH₃ C₂H₅ H H

143-145 18 CH₃ C₂H₅ Cl H

124-125 19 CH₃ C₂H₅ H H

132-133 20 CH₃ C₂H₅ Cl H

142-143 21 CH₃ C₂H₅ H H

143-144 22 CH₃ C₂H₅ Cl H

155-156 23 CH₃ C₂H₅ H H

151-153 24 CH₃ C₂H₅ H H

124-126 25 CH₃ C₂H₅ H H

122-123 26 CH₃ C₂H₅ H H

126-127 27 CH₃ C₂H₅ H H

122-123 28 CH₃ C₂H₅ H H

96-97 29 CH₃ C₂H₅ H H

91-93 30 CH₃ C₂H₅ H H

107-108 31 CH₃ C₂H₅ F H

124-125 32 CH₃ C₂H₅ H H

1.5623/25.0 33 CH₃ C₂H₅ H H

109-110 34 CH₃ C₂H₅ H CH₃

81-82 35 CH₃ C₂H₅ F H

105-106 36 CH₃ C₂H₅ Cl H

93-95 37 CH₃ C₂H₅ H H

114-116 38 CH₃ C₂H₅ Cl H

117-118 39 CH₃ C₂H₅ H H

1.5523/23.0 40 CH₃ C₂H₅ Cl H

96-97 41 CH₃ C₂H₅ H H

95-96 42 CH₃ C₂H₅ Cl H

106-107 43 CH₃ C₂H₅ H H

95-96 44 CH₃ C₂H₅ H CH₃

122-123 45 CH₃ C₂H₅ H H

 99-100 46 CH₃ C₂H₅ Cl H

108-109 47 CH₃ C₂H₅ H H

113-114 48 CH₃ C₂H₅ Cl H

106-107 49 CH₃ C₂H₅ H H

118-119 50 CH₃ C₂H₅ H H

163-164 51 CH₃ C₂H₅ Cl H

136-137 52 CH₃ C₂H₅ H H

119-121 53 CH₃ C₃H₅ H H

141-143 54 CH₃ C₂H₅ H H

154-156 55 CH₃ C₂H₅ H CH₃

147-150 56 CH₃ C₂H₅ H H

1.5865/25.0 57 CH₃ i-C₃H₇ Br H

142-143 58 CH₃ CF₃ H H

153-154 59 C₂H₅ C₂H₅ H H

127-128 60 i-C₃H₇ C₂H₅ H H

1.5520/25.0 61 CH₃ C₂H₅ H H

1.5530/23.0 62 CH₃ C₃H₅ H H

1.5671/25.0 63 CH₃ C₂H₅ H H

81-83 64 CH₃ C₂H₅ F H

101-104 65 CH₃ C₂H₅ H H

87-89 66 CH₃ C₂H₅ H H

1.5476/23.0 67 CH₃ C₂H₅ H H

123-124 68 CH₃ CH₃ H H

111-112 69 CH₃ i-C₃H₇ H H

120-122 70 CH₃

H H

 99-100 71 CH₃ CH₃ H H

88-89 72 CH₃ C₂H₅ Cl H

106-107 73 CH₃ C₂H₅ H H

117-118 74 CH₃ C₂H₅ H H

155-157 75 CH₃ C₂H₅ H H

130-131 76 CH₃ C₂H₅ H H

167-168 77 CH₃ C₂H₅ H H

245-247 78 CH₃ C₂H₅ H H

140-141 79 CH₃ C₂H₅ Cl H

154-156 80 CH₃ C₂H₅ H H

102-104 81 CH₃ CH₃ H H

128-129 82 CH₃ C₂H₅ Cl H

122-123 83 CH₃ C₂H₅ H H

155-160 84 CH₃ n-C₃H₇ H H

131-135 85 CH₃ t-C₄H₉ H H

123-125 86 CH₃ CH₃ CH₃O H

75-77 87 CH₃ CH₃ n-C₃H₇O H

51-54 88 CH₃ CH₃ CHF₂O H

136-138 89 CH₃ C₂H₅ H H

209-211 90 CH₃ C₂H₅ H H

139-141 91 CH₃ C₂H₅ H H

242-245 92 CH₃ C₂H₅ H H

162-164 93 CH₃ C₂H₅ H H

152-154 94 CH₃ C₂H₅ H H

146-147 95 CH₃ C₂H₅ H H

131-136 96 CH₃ CH₃O H H

124-125 97 CH₃ C₂H₅O H H

104-105 98 CH₃ i-C₃H₇O H H

1.5480/25.0 99 CH₃ CHF₂O H H

137-139 100 CH₃ CH₃ Cl H

117-118 101 CH₃ n-C₃H₇O H H

81-83 102 CH₃ CH₃ NO₂ H

198-199 103 CH₃ H H H

123-125 104 CH₃

H

155-156 105 CH₃

H

157-159 106 CH₃

H

194-195 107 CH₃

H

190-192 108 CH₃ CH₃ H H

150-151

Example 3

Synthesis of 4-(4-difluoromethoxyphenyl)benzylamine:

A mixture of 4-cyano-4′-difluoromethoxybiphenyl (15.0 g), Raney-nickelR-100 (15 g) and aqueous 28% ammonia (15.0 ml) was shaken in hydrogenatmosphere at 50° C. for 4 hours. After the reaction mixture was cooledto ambient temperature, Raney-nickel was filtered off. The solvent wasdistilled off under reduced pressure, to obtain 13.8 g of Compound No.113 described in Table-2. The melting point was 109 to 11° C.

Example 4

Synthesis of 4-(4-trifluoromethoxy)-α-methylbenzylamine:

A mixture of 4-(4-trifluoromethoxyphenyl)acetophenone oxime (8.8 g),Raney-nickel R-100 (10 g) and aqueous 28% ammonia (10.0 ml) was shakenin hydrogen atmosphere at 50° C. for 3 hours. After the reaction mixturewas cooled to ambient temperature, Raney-nickel was filtered off. Thesolvent was distilled off under reduced pressure, to obtain 7.61 g ofCompound No. 117 described in Table-2. The melting point was 70 to 74°C.

Example 5

Synthesis of 4-(4-trifluoromethoxyphenyl)benzylamine Hydrochloride:

To a solution (20 ml) of 4-(4-trifluoromethoxyphenyl)benzylamine (5 g)in methanol, 12N hydrochloric acid (3.0 ml) was added, followed byagitation at ambient temperature for 2 hours, The solvent was distilledoff under reduced pressure. The resulting residue was rinsed withmethanol, to obtain 4.8 g of Compound No. 116 described in Table-2. Themelting point was 252 to 254° C.

Example 6

According to the methods described in Examples 3 to 5, the compoundsdescribed in Table-2 were synthetically prepared. TABLE 2

Compound No. R³

Y m.p.(° C.) or nD/(° C.) 109 H

— 1.5459/23.0 110 H

— 1.5530/23.0 111 H

— 143-145 112 H

— 109-110 113 H

— 109-110 114 H

HCl 220-225 115 H

— 80-82 116 H

HCl 252-254 117 CH₃

— 70-74 118 H

— 1.5430/23.0 119 H

— 1.5323/23.0 120 H

— 1.4911/23.0 121 H

HCl 176-180 122 H

— 1.5488/23.0 123 H

— 1.5030/23.0 124 H

— 1.5350/23.0 125 H

HCl 302-303 126 H

— 1.5540/23.0 127 H

— 87-89 128 H

— 1.5140/25.0 129 H

— 1.5531/25.0 130 H

— 1.5380/23.0 131 H

— 1.5273/25.0 132 H

— 1.5222/25.0 133 H

— 1.5301/23.0*Compound No.130 b.p. = 134-135° C./1 mmHg

Hereinbelow, Formulation Examples containing the compound of the presentinvention as the active ingredient are described, which are insecticidesand miticides for agriculture and horticulture and floriculture.However, the mode for carrying out the present invention is not limitedto those described below.

Formulation Example 1

Hydrates:

Twenty parts by weight of the compound of the present invention, 20parts by weight of Carplex #80 (trade name; white carbon; manufacturedby Shionogi & Co., Ltd.), 52 parts by weight of ST kaolin clay (tradename; kaolinite; manufactured by Tuchiya Kaolin Co., Ltd.), 5 parts byweight of Solpol 9047K (trade name; anionic surfactant; manufactured byToho Chemical, Co., Ltd.) and 3 parts by weight of Lunox P56L (tradename; anionic surfactant; Toho Chemical Co., Ltd.) were blendedtogether, uniformly mixed together and ground, to obtain hydratescontaining the active ingredient at a content of 20% by weight.

Formulation Example 2

Powders;

Two parts by weight of the compound of the present invention, 93 partsby weight of clay (manufactured by Nippon Talc Co., Ltd.), and 5 partsby weight of Carplex #80 (trade name; white carbon; manufactured byShionogi Pharmaceutical Co., Ltd.) were uniformly mixed together andground, to obtain powders containing the active ingredient at a contentof 2% by weight.

Formulation Example 3

Emulsions:

Twenty parts by weight of the compound of the present invention weredissolved in a mixture solvent of 35 parts by weight of xylene and 30parts by weight of dimethylformamide, followed by addition of 15 partsby weight of Solpol 3005X (trade name; a mixture of a nonionicsurfactant and an anionic surfactant; Toho Chemical Co., Ltd.), toobtain emulsions containing the active ingredient at a content of 20% byweight.

Formulation Example 4

Flowable Agents:

Thirty parts by weight of the compound of the present invention, 5 partsby weight of Solpol 9047K, 3 parts by weight of Sorbon T-20 (trade name;nonionic surfactant; Toho Pharmaceutical Co., Ltd.), 8 parts by weightof ethylene glycol and 44 parts by weight of water were ground by wetprocess with Dinomill (manufactured by Sinmaru Enterprise, Co., Ltd.).Ten parts by weight of an aqueous 1% by weight solution of xanthan gum(naturally occurring polymer) were added to the resulting slurrymixture, followed by thorough mixing and grinding, to obtain flowableagents containing the active ingredient at a content of 20% by weight.

Test examples of fungicides and bactericides, insecticides and miticidesfor agriculture and horticulture and floriculture are shown below, whichcontain the compound of the present invention as the active ingredient.However, the mode for carrying out the present invention is not limitedto those described below.

Test Example 1

Fungicidal and Bactericidal Effect on Wheat Powdery Mildew:

Compound (III) disclosed in JP-A-64-25763, tebufenpyrade and variouscompounds in accordance with the present invention were individuallyprepared into preparations in the same manner as in Formulation 3 Theresulting preparations were diluted to given concentrations and sprayedon the stems and leave of a wheat plant (species: Norin No.61) at theone-leaf to 2-leaf stage as grown in a pot of a 6-cm diameter, at aratio of 10-ml volume per one pot. After drying the chemicalpreparations in air, the wheat plant was exposed to the spore collectedfrom wheat leave afflicted with Erypsiphe graminis as the microorganismcausing wheat powdery mildew, for inoculation. Then, the plant was leftto stand alone in a green house for 7 to 10 days.

Evaluation was carried out follows. The ratio of the diseased area ofeach leaf was examined to calculate the control ratio according to thefollowing formula. The results are shown in Table 3 (in the table,Compound Nos. correspond to Compound Nos. in Table-1.)

-   -   Control ratio (%)    -   =[(mean ratio of diseased areas in non-treated lot)    -   −(mean ratio of diseased areas in treated lot)]×    -   ×100

/ (mean ratio of diseased areas in non-treated lot) TABLE 3 Compound No.Concentration (ppm) Control Ratio (%) 3 500 100 4 500 100 5 500 100 6500 100 7 500 100 13 500 100 17 500 100 21 500 100 25 500 100 30 500 10031 500 100 34 500 100 35 500 100 36 500 100 37 500 100 39 500 100 40 500100 41 500 100 42 500 100 45 500 100 46 500 100 47 500 100 48 500 100 49500 100 54 500 100 63 500 100 64 500 100 68 500 100 69 500 100 70 500100 71 500 100 72 500 100 78 500 100 80 500 100 81 500 100 82 500 100 84500 100 85 500 100 86 500 100 87 500 100 88 500 100 90 500 100 91 500100 92 500 100 98 500 100 101 500 100 (III) 500 0 tebufenpyrade 500 77

Test Example 2

Fungicidal and Bactericidal Effect on Wheat Rust:

Compound (III) disclosed in JP-A-64-25763 and various compounds inaccordance with the present invention were individually prepared intopreparations in the same manner as in Preparation 3. The resultingpreparations were diluted to given concentrations and sprayed on thestems and leave of a wheat seedling (species: Norin No.61) at theone-leaf to 2-leaf stage as grown in a pot of a 6-cm diameter, at aratio of 10-ml volume per one pot. After drying the chemicalpreparations in air, a spore suspension prepared by grinding the sporecollected from wheat leave afflicted with Puccinia recondita as themicroorganism causing wheat rust was sprayed on the wheat plant, forinoculation. Then, the plant was left to stand alone in a moist chamberat 22° C. for 15 hours. Subsequently, the plant was left to stand in awater pool in a green house for 7 days.

Evaluation was carried out by examining the ratio of the diseased areaof each leaf to calculate the control ratio by the same method as inTest Example 1.

The results are shown in Table 4 (in the table, Compound Nos. correspondto Compound Nos, in Table-1.) TABLE 4 Compound No. Concentration (ppm)Control Ratio (%) 3 500 100 4 500 100 5 500 100 6 500 100 7 500 100 17500 100 21 500 100 25 500 100 30 500 100 34 500 100 35 500 100 36 500100 39 500 100 40 500 100 41 500 100 45 500 100 46 500 100 49 500 100 54500 100 63 500 100 64 500 100 68 500 100 69 500 100 70 500 100 71 500100 72 500 100 80 500 100 86 500 100 90 500 100 (III) 500 0

Test Example 3

Fungicidal and Bactericidal Effect on Larvae of Spodoptera litura:

Compound (III) disclosed in JP-A-64-25763 and various compounds inaccordance with the present invention were individually prepared intoinsecticide preparations according to the formulation of FormulationExample 1. The resulting insecticides of the present invention(hydrates) were diluted with water, where chopped cabbage leave (adiameter of 6 cm) were then immersed for one minute. After immersion andsubsequent drying in air, the cabbage leave were placed in a plastic cup(inner diameter of 7 cm), where five larvae each of 3rd instarSpodoptera litura were left (twice in duplicate per one concentration).The plastic cup was kept in a thermostat at 25° C. Five days after thelarvae were left in the plastic cup, the death and agony of these larvaewere examined, to calculate the insecticide activity (%) while anagonizing insect was counted as 0.5 insect death. The results are shownin Table 5 (in the table, Compound Nos. correspond to Compound Nos. inTable-1.) TABLE 5 Compound No. Concentration (ppm) Insecticide Activity(%) 3 500 100 5 500 100 6 500 100 7 500 100 15 500 100 37 500 100 39 500100 41 500 100 42 500 100 47 500 100 49 500 100 52 500 100 55 500 100 70500 100 78 500 100 86 500 100 90 500 100 100 500 100 107 500 100 (III)500 20

Test Example 4

Miticidal effect on adult Tetranychus urticae Koch

The stem part of a Phaseolus seedling with one fresh first leafremaining thereon was inserted in a test tube (a volume of 50 ml)containing water, where 15 female adult Tetranychus urticae Koch per oneleaf was then inoculated. One day after the inoculation, the leavedeposited with Tetranychus urticae Koch were immersed in and treatedwith an aqueous dilution of each of miticides (emulsions) individuallyproduced from Compound (III) disclosed in JP-A-64-25763, tebufenpyradeand various compounds of the present invention according to theformulation for Formulation Example 3 (for about 5 seconds) (single oneconcentration, duplicate) The resulting test tubes were kept in athermostat at 25° C. Five days after the treatment, the number of thefemale adult Tetranychus urticae Koch was counted on the Phaseolusleave, to calculate the adult death ratio (%) based on the aboveresults. The results are shown in Table-6 (Compound Nos. in the tablebelow correspond to Compound Nos. in Table-1). TABLE 6 Compound No.Concentration (ppm) Adult death ratio (%) 2 500 100 4 500 100 5 500 1006 500 100 7 500 100 11 500 100 17 500 100 18 500 100 22 500 100 30 500100 31 500 100 32 500 100 33 500 100 35 500 100 36 500 100 37 500 100 38500 100 39 500 100 12.5 100 3.1 100 0.8 100 40 500 100 41 500 100 42 500100 43 500 100 46 500 100 47 500 100 48 500 100 49 500 100 50 500 100 52500 100 53 500 100 55 500 100 63 500 100 68 500 100 69 500 100 70 500100 71 500 100 78 500 100 79 500 100 80 500 100 81 500 100 82 500 100 83500 100 84 500 100 85 500 100 86 500 100 87 500 100 88 500 100 96 500100 98 500 100 100 500 100 104 500 100 105 500 100 106 500 100 107 500100 108 500 100 (III) 500 15 tebufenpyrade 12.5 100 3.1 80 0.8 0

While the invention has been described in detail with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

The present application is based on a Japanese patent application filedon Apr. 6, 2001 (Japanese Patent Application 2001-108116), the entirecontents of which are incorporated hereinto by reference.

Industrial Applicability

The pyrazolecarboxamides of the present invention have such greateffects on the control of bacterial strains, hazardous insects and mitesthat the pyrazolecarboxamides function as great insecticides andmiticides for agriculture, forestry and disease control. Additionally,the pyrazolecarboxamides of the present invention are promising as acontrol agent of various hazardous biological organisms for livestockindustry, fishery, or storage of various products and public hygiene.

1. Pyrazolecarboxamide represented by the following formula (I):

wherein R¹ represents C₁-C₅ alkyl, R² represents C₁-C₅ alkyl, C₁-C₅haloalkyl, C₁-C₅ alkoxy or C₁-C₅ haloalkoxy, R³ represents hydrogen orC₁-C₃ alkyl, R⁴ represents C₁-C₅ alkyl, C₁-C₅ haloalkyl, C₁-C₅ alkoxy,C₁-C₅ haloalkoxy or halogen, m is an integer of 0 to 4; R⁵ representsalkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio,alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl,halogen, cyano, formyl, vinyl, alkoxycarbonyl, haloalkoxycarbonyl,acetyl, hydroxycarbonyl, alkylcarbamoyl or a group represented by

wherein R⁷ and R⁸ each represents hydrogen or C₁-C₅ alkyl, n representsan integer of 1 to 5, X represents hydrogen, C₁-C₃ alkyl, C₁-C₃ alkoxy,halogen, C₁-C₃ haloalkoxy or nitro, or R² and X may be taken together toform

wherein R⁹ represents hydrogen or C₁-C₃ alkyl.
 2. Thepyrazolecarboxamide according to claim 1, wherein R¹ in formula (I) ismethyl.
 3. The pyrazolecarboxamide according to claim 1, wherein R² informula (I) is ethyl.
 4. The pyrazolecarboxamide according to claim 1,wherein R⁵ in formula (I) is C₁-C₅ haloalkyl or C₁-C₅ haloalkoxy.
 5. Thepyrazolecarboxamide according to any one of claims 1 to 4 claim 1,wherein R³ in formula (I) is hydrogen.
 6. The pyrazolecarboxamideaccording to claim 1, wherein X in formula (I) is hydrogen.
 7. Thepyrazolecarboxamide according to claim 1, wherein, in formula (I), m isan integer of 0 to 2 and n is 1 or
 2. 8. Phenylbenzylamine representedby the following formula (II):

wherein R³ represents hydrogen or C₁-C₃ alkyl, R⁴ represents C₁-C₅alkyl, C₁-C₅ haloalkyl, C₁-C₅ alkoxy, C₁-C₅ haloalkoxy or halogen, m isan integer of 0 to 4; n represents an integer of 1 to 5; and R⁶represents haloalkyl or haloalkoxy, or an acid addition salt thereof. 9.A pest control agent comprising the pyrazolecarboxamide according toclaim 1 as an active ingredient.
 10. A fungicidal and bactericidal agentcomprising the pyrazolecarboxamide according to claim 1 as an activeingredient.
 11. An insecticidal and miticidal agent comprising thepyrazolecarboxamide according to claim 1 as an active ingredientthereof.